Surface-coating compositions that contain n1-(substituted ethyl)indazoles

ABSTRACT

COMPOUNDS THAT HAVE THE STRUCTURAL FORMULA   1-(X-CH2-CH2-),3-Z,5-Y,7-Y&#39;&#39;-1H-INDAZOLE   WHEREIN X REPRESENTS HALOGEN, -SCN, -OR, OR -N=R&#39;&#39;; Y AND Y&#39;&#39; EACH REPRESENTS HYDROGEN, HALOGEN, LOWER ALKYL, NITRO, AMINO, ACOYLAMINO, AROYLAMINO, (HALOBENZYLIDE) AMINO, OR-N=R&#39;&#39;; Z REPRESENTS HYDROGEN, HALOGEN, ACOYLAMINO, OR-N=R&#39;&#39;; R REPRESENTS HYDROGEN, ALKYL HAVING 1 TO 12 CARBON ATOMS, HALOALKYL HAVING 1 TO 4 CARBON ATOMS, PHENYL, OR SUBSTITUTED PHENYL WHEREIN THE SUBSTITUENT IS HALOGEN, HYDROXYL, ALKYL, OR NITRO; AND R&#39;&#39; REPRESENTS AN ALKYLENE GROUP HAVING 1 TO 8 CARBON ATOMS, ARE USED TO PROTECT SURFACE-COATING COMPOSITIONS FROM DETERIORATION RESULTING FROM ATTACK BY BACTERIA AND FUNGI. ILLUSTRATIVE OF THESE N1-(SUBSTITUTED ETHYL)INDAZOLES IN N1-(2-HYDROXYETHYL)-5-NITRO-INDAZOLE.

United States Patent i SURFACE-COATING COMPOSITIONS THAT CON- TAIN N-(SUBSTITUTED ETHYL)INDAZOLES Pasquale P. Minieri, Woodside, N.Y.,assignor to Tenneco Chemicals, Inc.

No Drawing. Application Feb. 7, 1972, Ser. No. 224,294, which is acontinuation-in-part of applications Ser. No. 689,812, Dec. 12, 1967,now Patent No. 3,641,050, and Ser. No. 141,999, May 10 1971, now PatentNo. 3,741,- 979. Divided and this application Apr. 20, 1973, Ser.

Int. Cl. C09d /14 US. Cl. 106-17 11 Claims ABSTRACT OF THE DISCLOSURECompounds that have the structural formula wherein X represents halogen,SCN, OR, or N=R; Y and Y each represents hydrogen, halogen, lower alkyl,nitro, amino, acoylamino, aroylamino, (halobenzylidene) amino, or N=R; Zrepresents hydrogen, halogen, acoylamino, or N=R; R represents hydrogen,alkyl having 1 to 12 carbon atoms, haloalkyl having 1 to 4 carbon atoms,phenyl, or substituted phenyl wherein the substituent is halogen,hydroxyl, alkyl, or nitro; and R represents an alkylene group having 1to 8 carbon atoms, are used to protect surface-coating compositions fromdeterioration resulting from attack by bacteria and fungi. Illustrativeof these N -(substituted ethyl)indazoles is N-(2-hydroxyethyl)-5-nitro-indazole.

This is a division of my copending application Ser. No. 224,294, whichwas filed on Feb. 7, 1972 and which is a continuation-in-part ofcopending applications Ser. No. 689,812, which was filed on Dec. 12,1967, now US. Pat. No. 3,641,050 and Ser. No. 141,999, which was filedon May 10, 1971, now US. Pat. No. 3,741,979.

This invention relates to surface-coating compositions that haveimproved resistance to deterioration resulting from attack by fungi,bacteria, and other microorganisms. More particularly, it relates tosurface-coating compositions that contain biocidal amounts of N-(substituted ethyl) indazoles.

It is well known in the art that paints and varnishes often haveinadequate resistance to the action of microorganisms. Some of thesecoating compositions, such as enamels and house paints, contain as theirresinous binders drying oils, oleoresinous varnishes, or alkyd resins,which are subject to attack by fungi and bacteria. Others, for example,aqueous dispersions of water-insoluble synthetic linear polymers,generally contain as plasticizers and thickeners materials that havetheir origin in animal or vegetable sources and that render thecompositions susceptible to mildew. The resulting deterioration of thesurface-coating compositions seriously hinders their full scaleutilization, particularly in those areas and in those applications thatare conducive to such attack.

Various biocidal materials have been suggsted for use in surface-coatingcompositions, but none has proven entirely satisfactory in thisapplication. Some do not provide the required prolonged protectionagainst attack by microorganisms, while others undergo sulfide stainingand still others hydrolyze in alkaline aqueous paint systems or separatefrom the applied coating by migration, volatiliza- Patented July 30,1974 tion, or leaching once the coating has been spread in a thin layerover the surface to be protected.

This invention rel-ates to biocides that are of particular value insurface-coating compositions. These biocides, which are thoroughlycompatible with the resinous binders that commonly are used insurface-coating compositions and which are resistant to sulfidestaining, provide excellent and prolonged resistance to deteriorationresulting from attack by fungi and other microorganisms withoutadversely afiecting the color, p-H, viscosity, and other physicalproperties of the surface-coating compositions.

The biocidal compounds that are used in the surfacecoating compositionsof this invention are N-( substituted ethyl)-indazoles. These compoundsmay be represented by the structural formula wherein X representschlorine, bromine, fluorine, iodine, thiocyanato, OR, or N=R; Y and Yeach repre sents hydrogen, chlorine, bromine, fluorine, iodine, alkylhaving 1 to 4 carbon atoms, nitro, amino, acoylamino, aroylamino,(halobenzylidene)-amino, or N=R; Z represents hydrogen, chlorine,bromine, fluorine, iodine, acoylamino, or N=R; R represents hydrogen,alkyl having 1 to 12 carbon atoms, chloroalkyl having 1 to 4 carbonatoms, bromoalkyl having 1 to 4 carbon atoms, fluoroalkyl having 1 to 4carbon atoms, iodoalkyl having 1 to 4 carbon atoms, phenyl,chlorophenyl, bromophenyl, fiuorophenyl, iodophenyl, hydroxyphenyl,alkylphenyl, or nitrophenyl; and R represents an alkylene group having 1to 8 carbon atoms.

Illustrative of the compounds of this invention are the following:

N Z-hydroxyethyl 3 chloroindazole;

N Z-hydroxyethyl 3chloro-S-nitroindazole;

N 2-hydroxyethyl 3 S-dibromoindazole;

N 2-hydroxyethyl 5 ,7-dichloroindazole;

N -(2-bromoethyl) -5,7-dibromoindazole;

N (2-fiuoroethyl -3methyleneiminoindazole;

N -(2-iodoethyl) 3 acetaminoindazole;

N (2-thiocyanatoethyl 5-methyleneiminoindazole;

N 2-thiocyanatoethyl 5-methyl-"7-nitroindazole;

N -(2-methyleneiminoethyl 5-acetaminoindazole;

N Z-piperidinoethyl 5- 3 ,4-dichlorobenzylideue) aminoindazole;

N -(2-methoxyethy1)5-ethyleneiminoindazoleg N (2-chloroethoxyethyl5-piperidinoindazole;

N 2-bromobutoxyethyl) indazole;

N (Z-phenoxyethyl 5-aminoindazole;

N [2- (m-nitrophenoxy ethyl] 3-chloroindazole;

N [2- (p-tert.butylphenoxy) ethyl] 5-methyl-7-chloroindazole;

N 2-butoxyethyl 5-benzaminoindazole;

N [2- (o-hydroxyphenoxy ethyl] -3,5-dichloroindazole;

and the like.

The most efl'ective of these compounds in surfacecoating compositionsare those in which X represents hydroxyl or halogen; Y and Y' eachrepresents hydrogen, halogen or nitro; and Z represents hydrogen orhalogen. The following are examples of these preferred compounds:

N 2-hydroxyethyl ind azole; N -(2-hydroxyethyl)3chloro-S-nitroindazole;N 2-hydroxyethyl -5,7-dichloroindazole; N (Z-hydroxyethyl)-5,7-dibromoindazo1e;

3 N Z-hydroxyethyl) -3,5,7-trichloroindazole; N -(2-chloroethyl) -3-chloroindazole; N 2-chloroethyl) -5-chloroindazole; N 2-bromoethyl) -3,5 ,7 -tribromoindazole; N -(2-fluoroethy1)-5,7-difiuoroindazole; N2-chloroethyl -5 ,7 -dichloroindazole; N 2-iodoethyl -5,7-diiodoindazole; N -(2-chloroethyl) -5-nitroindazole; and N2-chloroethyl -3-chloro-5-nitroindazole.

The N -(substituted ethyl)indazoles of this invention may be prepared byany suitable and convenient procedure. For example, they may be preparedby heating the appropriate substituted indazole with a compound thatwill react with it to form the desired N -(substituted ethyl)indazole.Thus, the N -(2-hydroxyethyl)indazoles may be prepared by heating asubstituted indazole with ethylene carbonate. The N -(2-chloroethyl)compounds are formed by heating the corresponding N -(2-hydroxyethyl)compounds with thionyl chloride, and the N -(2- thiocyanatoethyl)compounds are prepared by heating the N -(2-chloroethyl) compounds withpotassium thiocyanate. The reactions are generally carried out in asolvent such as benzene, toluene, xylene, acetone, pyridine, ethanol, orethylene dichloride, at the reflux temperature of the reaction mixture.

The N -(substituted ethyl)indazoles can be used to impart fungal andbacterial resistance to a Wide variety of surface-coating compositionsincluding both organic solvent-based and water-based systems.

In a preferred embodiment of the invention, the N -(substituted ethyl)indazoles are used as preservatives for surface-coating compositionsthat are aqueous dispersions that contain about percent to 60 percent byweight of a water-insoluble linear addition polymer and/ or anoleoresinous binder. The aqueous dispersions of synthetic linearaddition polymers are ordinarily prepared by the emulsion polymerizationof ethylenically-unsaturated compounds, especially those ofmonoethylenicallyunsaturated character, although butadiene,chlorobutadiene, and isoprene may be used to some extent. Illustrativeof the synthetic linear addition polymer that can be used as theresinous binder in the aqueous dispersions are polyvinyl acetate;polyvinyl butyrate; polyvinyl chloride; copolymers of vinyl acetate withacrylonitrile; copolymers of vinyl chloride with vinyl acetate orvinylidene chloride; polyethylene; polyisobutylene; polystyrene;copolymers of styrene with maleic anhydride or butadiene; copolymers ofacrylonitrile with butadiene; copolymers of methacrylic acid esters ofalcohols having 1 to 8 carbon atoms with vinyl acetate, vinyl chloride,acrylonitrile, or styrene; copolymers of acrylic acid esters of alcoholshav-= ing 1 to 8 carbon atoms with vinyl acetate, vinyl chloride,acrylonitrile, or styrene; and mixtures thereof. Suitable oleoresinousbinders include drying oils, such as linseed oil, tung oil, soybean oil,dehydrated castor oil, safflower oil, or fish oil, bodied drying oils;blends of drying oils or bodied drying oils with a resin component suchas limed rosin, an ester gum, or phenolic resin; oleoresinous varnishesformed by heating one of the aforementioned resins with one or moredrying oils or bodied drying oils; alkyd resins, which are resinousproducts resulting from the reaction of a polyhydric alcohol, such aspentaerythritol or glycerol, with a dicarboxylic acid, such as phthalicanhydride, and fatty acids; and mixtures thereof. The addition to suchsurface-coating compositions of as little as 0.10 percent by weight ofone or more of the biocidal compounds of this invention will bring aboutan appreciable improvement in the resistance of the composition toattack by bacteria. Three percent or more of the biocidal compounds canbe used, but these larger amounts ordinarily do not provide furtherimprovement in the properties of the surface-coating compositions andfor this reason are not usually used. It is generally preferred toincorporate 0.2 percent to 0.4 percent by weight of the biocidalcompounds into aqueous surface-coating compositions to protect them fromattack by bacteria.

In another preferred embodiment of this invention, the N -(substitutedethyl)indazoles are used to impart fungal and bacterial resistance todried films of protective or decorative coating compositions that havebeen applied to a surface. When they are added in the amount of about0.1 percent to about 3 percent, and preferably 0.5 percent to 2 percent,based on the weight of the surface-coating composition, these biocidalcompounds which are thoroughly compatible with the resinous binders thatare commonly used in surface-coating compositions and which areresistant to sulfide staining, provide excellent and prolongedresistance to deterioration resulting from attack by fungi, bacteria,and other microorganisms without adversely affecting the color, odor,viscosity, and other physical properties of the surface-coatingcompositions or of the dried films of these compositions.

Both organic solvent-based and water-based coating systems can bepreserved by incorporating into them the biocidal compounds of thisinvention. These compounds are of particular value as biocides incoatings that contain as their resinous binder an oleoresinous binderand/or a water-insoluble synthetic linear addition polymer ashereinbefore defined.

In addition to the resinous binder and the N -(substitutedethyl)indazole, the surface-coating compositions of this invention maycontain various auxiliary materials, such as pigments, extenders,solvents, dyes, defoaming agents, driers, emulsifying agents, dispersingagents, plasticizers, and the like in the amounts ordinarily used forthese purposes.

The N -(substituted ethyl)indazoles may be incor porated into thesurface-coating composition by any convenient procedure. For example,they can be combined with pigments and various other components to forma pigment phase that is then mixed With the resinous binder and water oran organic solvent to form the surfacecoating composition.Alternatively, they can be added to a composition that contains theresinous binder, pigment, and water or organic solvent. The biocidalcompound can be added as such to the other components of thesurface-coating composition, or they can be added as a solution in analcohol, ether, ketone or other solvent.

The invention is further illustrated by the following examples.

Example 1 -N -(2-hydroxyethyl)-3-chloroindazole was obtained. Thiscompound melted at 113-l26 C. and contained 53.69 percent C, 3.66percent H, and 16.15 percent N (calculated, 55.2 percent C, 4.6 percentH, and 14.2 percent N).

Example 2 The procedure described in Example 1 was repeated using5-chloroindazole in place of 3-chloroindazole. The N-(2-hydroxyethyl-S-chloroindazole obtained was an oil that contained52.8 percent C, 4.5 percent H, 13.9 percent N, and 18.0 percent Cl(calculated, 55.2 percent C, 4.6 percent H, 14.2 percent N, and 18.0percent Cl).

Example 3 The procedure described in Example 1 was repeated using3-chloro-5-nitroindazole in place of 3-chloroindazole. The N-(2-hydroxyethyl)-3-chloro-5-nitroindazole obtained melted at l13 C. andcontained 46.2 per cent C, 3.8 percent H, 19.1 percent N, and 12.6percent 5 6 C1 (calculated, 44.7 percent C, 3.8 percent H, 17.4 per-This paint had the following properties: cent N, and 14.7 percent CI).Viscosity: 72 K.U.

Examples 4 and 5 Brookfield Viscosity (#3 spindle, 60 r.p.m.): 1250 cps.

The following compounds were prepared by the proce- P I dure describedin Example 1: 5 Yellowness Index: 2.6

Analysis, percent Melting Found Calculated Example point number CompoundC H N 01 C H N 01 4 N -(2-hydroxyethylg-5-nitrolndazole 97-112 52.2 4.619 7 62.2 4.3 21.0 N -(2-hydroxyethy1 -3,5-dichloroindazole 46.1 2.7 125 31.5 46.7 3.5 12.1 30.7

Example 6 A. A polyvinyl acetate latex paint was prepared by mixingtogether the following materials: together the following a s:

Parts y Weight 20 Parts by Weight Water BaSiC Lead carbonate m: 2Aqueous solution of sodium salt of maleic Zinc Oxide 232anhydride/diisobutylene copolymer 24 Titanium dioxide (futile) 149Potassium pyrophosphate 3 Talc Long chain fatty acid alkanolamide 9 25 i-g1 Defoamer 6 Ethylene glycol 75 Bqdled lmseed 011 114 l%% Aqueoussolution of hydroxyethylcellu- Mineral Spirits l 375 Antiskinning AgentAqueous emulsion containing 55% 0 P y y Manganese naphthenate (6%) 2.27

acetate 129 Lead na hth t 24 n Diethyl ether of diethylene glycol .30 Pam e Titanium dioxide 690 Talc 345 Example 7 150 calcufm wetaslhcate IThe paints whose preparation was described in Example This paint had thefollowlng propertles as determined 6 were evaluated by means of an agarinfusion ay In s z i gi g ii b procedures: this test agar is inoculatedwith the test organism, the ated paint is placed in a well cut from thea ar and Brookfield Viscosit 4 s indle, 60 r. .m. 800c s. g y p P p 40after incubation at 28 C. and 85-95% relative humidity, the activity ofthe biocide is measured by zones of inhibi- Yellowness Index: 3.0

B. An acrylic latex paint was prepared by mixing to- C. An exteriorhouse paint was prepared by mixing tion. The biocidal compounds testedand the results ob gather the following materials; tained are given inthe table that follows. In this table Parts by ZO=Zone of inhibition inmm. 11% 'gggg 'gg ggggg""""""" 6 Zone of inhibition; n g w h 25% Aqueoussolution of sodium salt of maleic il g g of mhlbmonanhydride/diisobutylene copolymer 27 teste Defoamer 12 Bacteria: 2%Aqueous solution of hydroxyethylcellulose 300 ABacillus subtilisEthylene glycol 60 BA erobacter aerogenes Titanium dioxide 750CPseudom0nas aeruginosa Mica (waterground) 33g Fungi: Calcium carbonateAmmonium hydroxide (28%) 6 I ;f'f t 'l m Aqueous dispersion containing46% acrylic ester f 0 copolymer (66% ethyl acrylate, 32.5% methylF-Aspergzllus mger acrylate, and 1.5% acrylic acid) 1642 Activity of N-(2-substituted ethyl)indazoles as biocides in paints Biocidal activityEfleet on paint Bacteria Fungi Biocide Paint pH Color A B C D E 0 0 020-6 zo-s Example 2 Acrylic.... 9.2 Oil-white..- 0 0 0 20-2 ZO-l .6 B 0o 0 ZO-l ZO-l '1 gift oi i v hite zo-z Tr 20-1 9.313' T 0 0 0 Tr Example@35 2?" 7.1 E lie Ti 0 0 o 0 Oil White 0 0 What is claimed is:

1. A surface-coating composition that comprises (a) a water-insolubleresinous binder selected from the group consisting of oleoresinousbinders, synthetic linear addition polymers obtained by the vinylpolymerization of monoethylenically-unsaturated monomers, and mixturesthereof and (b) about 0.10 percent to 3 percent, based on the weight ofsaid composition, of a biocidal compound having the structural formulaII Y oHr-om-X wherein X represents halogen, OR, SCN, or N=R'; Y and Yeach represents hydrogen, halogen, lower alkyl, nitro, amino,acoylamino, aroylamino, (halobenzylidene) amino, or N=R'; Z representshydrogen, halogen, acoylamino, or N=R'; R represents hydrogen, alkylhaving 1 to 12 carbon atoms, haloalkyl having 1 to 4 carbon atoms,phenyl, or substituted phenyl wherein the substituent is halogen,hydroxyl, alkyl, or nitro; and R represents an alkylene group having 1to 8 carbon atoms. 2. A surface-coating composition as set forth inClaim 1 that contains 0.5 percent to 2 percent, based on the weight ofthe composition, of the biocidal compound.

3. A surface-coating composition as set forth in Claim 1 wherein thebiocidal compound has the structural formula wherein X representshydroxyl or halogen; Y" and Y each represents halogen, hydrogen, ornitro; and Z represents hydrogen or halogen.

4. A surface-coating composition as set forth in Claim 1 wherein thebiocidal compound is N -(2-hydroxyethyl)- S-chloroindazole.

5. A surface-coating composition as set forth in Claim 1 wherein thebiocidal compound is N -(2-hydroxyethyl)- 3-chloroindazole.

Y HzCHi-X wherein X represents halogen, OR, %CN, or -N=R'; Y and Y eachrepresents hydrogen, halogen, lower alkyl, nitro, amino, acoylamino,aroylamino, (halobenzylidene) amino, or N=R'; Z represents hydrogen,halogen, acoylamino, or N=R'; R represents hydrogen, alkyl having 1 to12 carbon atoms, haloalkyl having 1 to 4 carbon atoms, phenyl, orsubstituted phenyl wherein the substituent is halogen, hydroxyl, alkyl,or nitro; and R represents an alkylene group having 1 to 8 carbon atoms.

7. An aqueous surface-coating composition as set forth in Claim 6 thatcontains 0.2 percent to 0.4 percent by weight of said biocidal compound.

8. The process of controlling the growth of fungi and othermicroorganisms in a surface-coating composition that contains awater-insoluble resinous binder selected from the group consisting ofoleoresinous binders, synthetic linear addition polymers obtained by thevinyl polymerization of monoethylenically-unsaturated monomers, andmixtures thereof that comprises incorporating in said composition about0.10 percent to 3 percent, based on the weight of said composition, of abiocidal compound having the structural formula wherein X representshalogen, OR, SCN, or N=R'; Y and Y each represents hydrogen, halogen,lower alkyl, nitro, amino, acoylamino, aroylamino, (halobenzylidene)amino, or N=R'; Z represents hydrogen, halogen, acoylamino, or N=R'; Rrepresents hydrogen, alkyl having 1 to 12 carbon atoms, haloalkyl having1 to 4 carbon atoms; phenyl, or substituted phenyl wherein thesubstituent is halogen, hydroxyl, alkyl, or nitro; and R represents analkylene group having 1 to 8 carbon atoms.

9. The process of Claim 8 wherein 0.5 percent to 2 percent, based on theweight of the composition, of the biocidal compound is incorporated intothe composition.

10. The process for preventing bacteria-caused spoilage in an aqueoussurface-coating composition that comprises incorporating in said aqueouscomposition 0.1 percent to 3.0 percent, based on the weight of saidcomposition, of a. biocidal compound having the structural formulawherein X represents halogen, OR, SCN, or N=R'; Y and Y' each representshydrogen, halogen, lower alkyl, nitro, amino, acoylamino, aroylamino,(halobenzylidene) amino, or N=R'; Z represents hydrogen, halogen,acoylamino, or N=R; R represents hydrogen, alkyl having 1 to 12 carbonatoms, haloalkyl having 1 to 4 carbon atoms, phenyl, or substitutedphenyl wherein the substit uent is halogen, hydroxyl, alkyl, or nitro;and R represents an alkylene group having 1 to 8 carbon atoms.

11. The process of Claim 10 wherein 0.2 percent to 0.4 percent by weightof the biocidal compound is incorporated into the aqueous composition.

References Cited UNITED STATES PATENTS 3,637,736 1/1972 Minieri 260310 CFOREIGN PATENTS 1,568,790 4/1969 France 260310 C 1,814,335 8/1969Germany 260-310 C 2,003,561 7/1970 Germany 2603 10 C OTHER REFERENCESAuwers et al.: Chem. Abs. 22, 1156 (1928). Pozharskii et al.: J. Gen.Chem. (U.S.S.R.) pp. 3409- 3411 (1964).

ALLAN LIEBERMAN, Primary Examiner T. DEBENDICTIS, SR Assistant ExaminerUS. Cl. X.R.

l06-l5 AF, 17, 18; 26029.6 RB, RW, WB, T, TA, MN, 45.8 N, 85.1, 85.5 N,86.1 R, 86.3, 86.7, 87.1, 88.7 F, 92.8 A, 94.8, 94.9 R, 310 C

